Dialkylzinc compositions having improved thermal stability

ABSTRACT

Acenaphthene compounds are added to dialkyl-zinc compositions to improve the thermal stability of the compositions.

BACKGROUND OF THE INVENTION

The present invention relates to dialkylzinc compositions having improved thermal stability. More particularly, the present invention relates to compositions comprising a dialkylzinc compound in admixture with a stabilizer which reduces the thermal decomposition rate of the dialkylzinc compound.

Dialkylzinc compounds, particularly diethylzinc, are known to be useful as polymerization catalysts in Ziegler-Natta type systems, as chemical intermediates as well as alkylating agents. In addition, diethylzinc has been found useful as a preservative for paper, which can be applied to existing books and the like to extend their useful life, as is reported in the October 1979 issue of "Chemical and Engineering News".

Unfortunately, however, the dialkylzinc compounds in addition to being pyrophoric and highly reactive with water, are thermally unstable and can decompose rapidly at elevated temperatures. The decomposition is exothermic, and could therefore become a "runaway reaction" unless special precautions are taken to prevent it. Thus, for example, a quantity of this material in storage could slowly increase in temperature, due to slow decomposition, until a point was reached where the decomposition rate increased to a level which could present a hazard.

It has been reported, for example, that the half-life of diethylzinc is 10 days at 120° C., about 1 day at 150° C. and only a few minutes at 200° C.

The thermal instability of these compounds has been a significant deterrent to their use because measures required to prevent the possibility of a runaway reaction sometimes outweigh the benefits to be achieved.

If, however, the dialkylzinc compounds could be stabilized against thermal decomposition so that their decomposition rates were more manageable, the use of these compounds would be far more attractive.

A need therefore exists for a method by which the thermal decomposition rates of dialkylzinc compounds can be reduced.

It has now been found that the addition of acenaphthene compounds to dialkylzinc compounds substantially reduces their rates of thermal decomposition.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a process for improving the thermal stability of a dialkylzinc compound represented by the formula

    R--Zn--R

wherein R represents an alkyl radical having from 1 to about 8 carbon atoms which comprises adding to the dialkylzinc compound an acenaphthene compound represented by the formula ##STR1## wherein each R¹ independently represents an alkyl radical, an olefin radical (conjugated with the aromatic moiety), an aryl radical or a substituted aryl radical, each having from 1 to about 12 carbon atoms, or hydrogen; in an amount sufficient to reduce the thermal decomposition rate of the dialkylzinc compound.

In accordance with another aspect of the present invention there is provided a dialkylzinc composition having improved stability against thermal decomposition comprising a dialkylzinc compound represented by the formula

    R--Zn--R

wherein R represents an alkyl radical having from 1 to about 8 carbon atoms, in admixture with an acenaphthene compound represented by the formula ##STR2## wherein each R¹ independently represents an alkyl radical, an olefin radical (conjugated with the aromatic moiety), an aryl radical or a substituted aryl radical, each having from 1 to about 12 carbon atoms, or hydrogen; said acenaphthene compound being present in an amount sufficient to reduce the thermal decomposition rate of said dialkylzinc compound.

DETAILED DESCRIPTION OF THE INVENTION

More in detail the dialkylzinc compounds which are stabilized in accordance with the present invention are represented by the formula

    R--Zn--R

wherein R represents an alkyl radical having from 1 to about 8 carbon atoms. These compounds include, but are not limited to dimethylzinc, diethylzinc, dibutylzinc, diisopropylzinc, and diisobutylzinc; although diethylzinc is preferred.

The acenaphthene compounds which are used are represented by the formula ##STR3## wherein each R¹ independently represents an alkyl radical, an olefin radical (conjugated with the aromatic moiety), an aryl radical or a substituted aryl radical, each having from 1 to about 12 carbon atoms, or hydrogen. A particularly preferred acenaphthene compound is acenaphthene.

The acenaphthene stabilizer can be added to the dialkylzinc by any conventional method, although the special handling requirements for the pyrophoric dialkylzinc compounds should be observed.

The amount of acenaphthene compound which is added is an amount which is sufficient to achieve the desired degree of stabilization. When, for example, the dialkylzinc compound being stabilized is diethylzinc, and the acenaphthene compound being used is acenaphthene, effective amounts of acenaphthene range from about 3% to about 5% by weight of diethylzinc.

The dialkylzinc compounds are shipped and used in industrial processes either neat, or diluted with hydrocarbon solvents. Hydrocarbon solutions of dialkylzinc compounds, particularly diethylzinc, typically range in concentrations from 5% up to 50% by weight. Solvents employed include, but are not limited to pentane, hexane, heptane, toluene and xylene. These solvents are, of course, dried before using because dialkylzinc compounds react with water.

The present invention may be practiced with either the neat dialkylzinc compound, or with the diluted forms.

In order that the present invention be more fully understood, the following examples are given by way of illustration. No specific details or enumerations contained therein should be construed as limitations except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

EXAMPLE I

A computer-controlled adiabatic calorimeter was used to determine the time required for the decomposition of diethylzinc to become a runaway reaction at various temperatures under adiabatic condition. The results are shown in Table I below.

                  TABLE I                                                          ______________________________________                                         TIME TO A RUNAWAY REACTION FOR THE                                             ADIABATIC DECOMPOSITION OF DIETHYL ZINC                                                       Time to a Runaway                                               Temperature °C.                                                                        Reaction                                                        ______________________________________                                          80            124.3        days                                                90            33.6         days                                               100            9.8          days                                               110            3            days                                               120            23.5         hours                                              130            7.5          hours                                              140            2.5          hours                                              ______________________________________                                    

This demonstrates the thermal instability of diethylzinc.

EXAMPLE 2

Samples of diethylzinc were placed in a 300 ml. glass lined autoclave equipped with an internal thermocouple and pressure transducer. The autoclave was then equilibrated to room temperature, after which it was heated to increase the temperature of the contents at the rate of about 5° per minute. The temperature and pressure inside the autoclave were continuously measured. The results of this test are summarized in table II below.

                                      TABLE II                                     __________________________________________________________________________     SUMMARY OF DIETHYL ZINC CONFINEMENT TESTS                                                                               Moles of Gas                                                                           Maximum Rate                           Exotherm*             Maximum Rate of                                                                          Generated per                                                                          of Gas                        Wt. of Diethyl-                                                                         Initiation                                                                           Maximum                                                                              Maximum Pressure                                                                         Pressure Rise                                                                            Mole of Generated                     zinc loaded (gms)                                                                       Temp. °C.                                                                     Temp. °C.                                                                     PSIG ATM  psi/sec                                                                            ATM/sec.                                                                             DEZ (1.)                                                                               moles/sec/mole                __________________________________________________________________________     15       248   285    680  47   270                                                                               18    2.4     1.01                          60       207   423   2750 188  1435                                                                               98    1.7     1.02                          __________________________________________________________________________      *In one previous run, the start of rapid pressure rise occured at              120° C.                                                                 (1.) DEZ: Diethylzinc                                                    

This example shows that the thermal decomposition of diethylzinc in confinement can result in substantial pressure generation. It also shows that the rate of pressure rise is dependent on sample size, but that the moles of gas generated per second for each mole of diethylzinc is independent of sample size and is on the order of 1.01 moles gas/second/mole of diethylzinc.

EXAMPLE III

Using the same equipment and procedure as in Example II, samples of diethylzinc were tested both with and without the additives listed in Table III. The results of these tests are shown in Table III.

                  TABLE III                                                        ______________________________________                                         SUMMARY OF DIETHYLZINC CONFINEMENT TESTS                                       ______________________________________                                                            Exo-                                                        Wt. of             therm                                                       Diethyl-           initi-   Maxi-                                              zinc               ation    mum   Maximum                                      load-     Addi-    Temp.    Temp. Pressure                                     Run  ed gms   tive     °C.                                                                            °C.                                                                           PSIG   ATM.                                ______________________________________                                         1    15       none     248    285   680    47                                  2    60       none     207    423   2750   188                                 3    60 5%    Acena-   200    413   940    65                                                phthy-                                                                         lene                                                             4    68˜5%                                                                             Acena-   208    499   1710   117                                               phthene                                                          5    60˜1%                                                                             Anthra-  193    405   >5000  341                                               cene                                                             6    23˜3%                                                                             Anthra-  ˜210                                                                            419   490    34                                                cene                                                             7    32˜5%                                                                             Anthra-  195    404   480    34                                                cene                                                             8    60 5%    Anthra-  210    383   850    59                                                cene                                                             ______________________________________                                                                 Moles                                                                          of Gas                                                 Wt. of                  gener-                                                 Di-                     ated     Maximum Rate                                  ethyl-                  per      of Gas                                        zinc     Maximum Rate of                                                                               mole of  Generation                                    loaded   Pressure Rise  Diethyl- Moles/sec/mole                                Run  gms     psi/sec  ATM/sec zinc   of Diethylzinc                            ______________________________________                                         1    15      270      18      2.4    1.01                                      2    60      1435     98      1.7    1.02                                      3    60      42       3       0.58   3.1 × 10.sup.-2                     4    68      293      20      0.83    0.176                                    5    60      1995     136     >3.2   1.42                                      6    23      ˜5 0.3     0.9    1.1 × 10.sup.-2                     7    32      4.3      0.3     0.6    6.5 × 10.sup.-3                     8    60      16       1.0     0.55   1.2 × 10.sup.-2                     ______________________________________                                    

This example demonstrates that the addition of 5% acenaphthene to the diethylzinc reduces the gas generation rate by a factor of about 5.

It will thus be seen that the process and composition set forth have desirable advantages over the prior art. Since certain changes may be made in the process and composition without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. 

I claim:
 1. A dialkylzinc composition having improved stability against thermal decomposition comprising a dialkylzinc compound represented by the formula

    R--Zn--R

wherein R represents an alkyl radical having from 1 to about 8 carbon atoms, in admixture with an acenaphthene compound represented by the formula ##STR4## wherein each R¹ independently represents an alkyl radical, an olefin radical (conjugated with the aromatic moiety), an aryl radical or a substituted aryl radical, each having from 1 to about 12 carbon atoms, or hydrogen; said acenaphthene compound being present in an amount sufficient to reduce the thermal decomposition rate of said dialkylzinc compound.
 2. The dialkylzinc composition of claim 1 wherein R represents an ethyl radical and said dialkylzinc compound is diethylzinc.
 3. The dialkylzinc composition of claim 2 wherein said acenaphthene compound is acenaphthene.
 4. The dialkylzinc composition of claim 3 wherein said acenaphthene is present in an amount ranging from about 3% to about 5% based on the weight of dialkylzinc compound present.
 5. A process for improving the thermal stability of a dialkylzinc compound represented by the formula

    R--Zn--R

wherein R represents and alkyl radical having from 1 to about 8 carbon atoms which comprises adding to said dialkylzinc compound an acenaphthene compound represented by the formula ##STR5## wherein each R₁ independently represents an alkyl radical, an olefin radical (conjugated with the aromatic moiety), an aryl radical or a substituted aryl radical, each having from 1 to about 12 carbon atoms, or hydrogen; in an amount sufficient to reduce the thermal decomposition rate of said dialkylzinc compound.
 6. The process of claim 5 wherein R represents an ethyl radical and said dialkylzinc compound is diethylzinc.
 7. The process of claim 6 wherein said acenaphthene compound is acenaphthene.
 8. The process of claim 7 wherein said acenaphthene is present in an amount ranging from about 3% to about 5% based on the weight of dialkylzinc present. 